(2-Chloro-4-cyanophenyl) (4-dialkylaminophenyl)-diazine dye useful for transfer printing

ABSTRACT

Dyes useful for transfer printing and having the formula ##STR1## in which X and Y are hydrogen or halogen, 
     Z is hydrogen or methyl, 
     R 1  is hydrogen, lower alkyl or alkoxy, 
     R 2  is hydrogen, chlorine, lower alkyl, alkoxy, alkanoylamino or pyrrolidonyl, and 
     R 3  and R 4  are alkyl optionally substituted by alkoxy, chlorine, alkanoyl or alkoxycarbonyl. The dyes are especially useful for the transfer printing of polyamides, giving prints having very good light and wet fastnesses.

This is a continuation, of application Ser. No. 643,108, filed Dec. 22, 1975, now abandoned.

The invention relates to the use of dyes of the formula (I): ##STR2## in which X is hydrogen, chloro or bromo;

Y is hydrogen or chloro;

Z is hydrogen or methyl;

R¹ is hydrogen, C₁ to C₄ alkyl, methoxy or ethoxy;

R² is hydrogen, C₁ to C₄ alkyl, chloro, methoxy, ethoxy, C₁ to C₄ alkanoylamino which may bear chloro, methoxy or ethoxy as a substituent of ##STR3## R³ is allyl, methallyl, C₁ to C₄ alkyl, C₁ to C₈ alkanoyloxy-C₂ - to C₄ -alkyl optionaly bearing chloro, methoxy or ethoxy as a subtituent in the alkanoyl or C₂ to C₄ alkyl bearing chloro or C₁ to C₈ alkoxycarbonyl as a substituent; and R⁴ is C₁ to C₄ alkyl, or C₂ to C₄ alkyl bearing C₁ to C₄ alkoxy or chloro as a substituent for transfer printing and also the new dyes.

The alkyl radical R¹ may be butyl, propyl or ethyl and particularly methyl.

Suitable radicals R², besides those already specified, are butyl, propyl, ethyl, formylamino, chloroacetylamino, methoxyacetylamino, ethoxyacetylamino and particularly methyl, acetylamino, propionylamino, n-butyrylamino or isobutyrylamino.

Examples of radicals R³ are: methyl, butyl, hexoxyethyl, β-ethylhexoxyethyl, hexoxypropyl, β-ethylhexoxypropyl, methoxybutyl, ethoxybutyl, formyloxyethyl, formyloxypropyl, chloroacetoxyethyl, chloroacetoxypropyl, ethoxyacetoxyethyl, ethoxyacetoxypropyl, hexanoyloxyethyl, hexanoyloxypropyl, β-ethylhexanoyloxyethyl, βethylhexanoyloxypropyl, methoxycarbonylpropyl, ethoxycarbonylpropyl, propoxycarbonylpropyl, butoxycarbonylproyl, hexoxycarbonylethyl, hexoxycarbonylpropyl, β-ethylhexoxycarbonylethyl, β-ethylhexoxycarbonylpropyl and particularly ethyl, propyl, chloroethyl, methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, n-propoxyethyl, isopropoxyethyl, n-propoxypropyl, isopropoxypropyl, acetoxyethyl, acetoxypropyl methoxyacetoxyethyl, methoxyacetoxypropyl, propionyloxyethyl, propionyloxypropyl, n-butyryloxyethyl, isobutyryloxyethyl, methoxycarbonylethyl, n-propoxycarbonylethyl, isopropoxycarbonylethyl, n-butoxycarbonylethyl, isobutoxycarbonylethyl or t-butoxycarbonylethyl.

Examples of radicals R⁴ are: methyl, butyl and chloroethyl and particularly ethyl, propyl, methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, isobutoxyethyl, methoxypropyl, ethoxypropyl, n-propoxyypropyl, isopropoxyethyl, n-butoxypropyl and isobutoxypropyl.

Particular technical importance attaches to dyes of the formula (Ia): ##STR4## in which R⁵ is hydrogen or methyl;

R⁶ is hydrogen, methyl, ethyl or C₂ to C₄ alkanoylamino;

R⁷ is C₂ to C₄ alkyl or C₂ to C₃ alkyl bearing C₁ to C₄ alkoxy, chloro, C₂ to C₄ alkanoylalkyl or C₁ to C₄ alkoxycarbonyl as a substituent; and

R⁸ is C₂ to C₄ alkyl or C₂ to C₄ alkyl bearing C₁ to C₄ alkoxy as a substituent.

One group of preferred dyes in that of formula (Ia) in which R⁵ is hydrogen and R⁶ is C₁ - to C₄ - alkyl.

Methyl or ethyl is particularly preferred for R⁶.

The dyes of formula (I) may be prepared by reacting a diazo compound of an amine of the formula (II): ##STR5## with a coupling component of the formula (III): ##STR6##

Dyes of the formula (I), some of which are new, are outstandingly suitable for transfer printing on substrates such as acrylonitrile polymers and preferably polyesters and polyamides.

For a long time there has been a demand for red dyes with which it is possible to obtain light-fast and wet-fast dyeings on polyamides by the transfer method. Light-fast red dyes transferable in particular onto polyamides have not hitherto been available. With the red compounds of the formula (I) it is possible to obtain on polyamides dyeings which are fast to both light and wet treatments and the wet fastness properties and the transferability can be preferentially influenced by the radicals R³ and R⁴. Radicals R³ and R⁴ preferably contain an ether oxygen atom or are preferably alkyl radicals.

Another group of preferred dyes in that of the formula (Ib) ##STR7## in which R⁹ is C₁ - to C₄ -alkyl; R⁷ is C₂ - to C₄ -alkyl, C₁ - to C₄ -alkoxy-C₂ - to C₃ -alkyl or β-chloroethyl; and R⁸ is C₂ - to C₄ -alkyl or C₁ - to C₄ -alkoxy-C₂ - to C₄ -alkyl. In formula (Ib), methyl is particularly preferred for R⁹.

Generally preferred dyes are those of the formula ##STR8## in which R¹ is hydrogen, C₁ - to C₄ -alkyl, methoxy or ethoxy,

R² is hydrogen, chlorine or C₁ - to C₄ -alkyl,

R³ is C₁ - to C₄ -alkyl or C₂ - to C₄ -alkyl substituted by C₁ - to C₆ -alkoxy, chloro, C₁ - to C₄ -alkanoyl, chloroacetyl, chloropropionyl, methoxyacetyl, ethoxyacetyl or C₁ - to C₄ -alkoxycarbonyl,

R⁴ is C₁ - to C₆ -alkyl or C₂ - to C₄ -alkyl substituted by C₁ - to C₄ -alkoxy or chloro and

Z is hydrogen or methyl. Those dyes of the formula (Ic) are especially preferred in which

R¹ is hydrogen, R² is C₁ - to C₄ -alkyl, and R³, R⁴ and Z have the same meanings as given under formula (Ic).

Transfer printing processes are known for example from French Pat. No. 1,223,330 and German Laid-Open Specification (DOS) No. 1,769,757 and auxiliary carriers and printing inks therefor are known from German Laid-Open Specifications (DOS) Nos. 1,771,812 and 1,771,813.

The following Examples illustrate the invention; parts and percentages are by weight unless stated otherwise.

EXAMPLE 1

13.5 parts of 3-chloro-4-aminobenzonitrile is stirred with 120 parts by volume of glacial acetic acid, then 24 parts by volume of 30% hydrochloric acid is introduced and the mixture is cooled to 5° to 10° C. 20 parts of ice is added followed by 27 parts by volume of a 23% sodium nitrite solution and the diazotization mixture is stirred for two hours at from 4° to 6° C. Excess nitrous acid is then destroyed as usual with sulfamic acid and the mixture obtained is allowed to flow into a solution, cooled to 4° to 8° C., of 18.8 parts of the coupling component of the formula: ##STR9## in 500 parts by volume of water and 8 parts by volume of 30% hydrochloric acid. The pH of the coupling mixture is then raised to 2.5 by adding 20% caustic soda solution (with simultaneous addition of 250 parts of ice for cooling). Coupling is rapidly over. The precipitated dye is filtered off, washed with water and dried. 30 parts of a red powder is obtained of the formula: ##STR10## It dissolves in dimethylformamide with a red coloration. 6 parts of this powder is dispersed with 94 parts of a mixture consisting of 5 parts of ethylcellulose, 70 parts of ethyl alcohol, 20 parts of ethyl acetate and 5 parts of ethyl glycol. The dye paste obtained is printed onto transfer paper and dried. The printed side of the paper is contacted with a cloth of a polyester, polyamide or polyacrylonitrile and heated for thirty seconds at 190° to 200° C. A full, yellowish red dyeing having good light and wet fastness properties is thus obtained on the cloth.

EXAMPLE 2

9.6 parts of 4-aminobenzonitrile is dispersed with 160 parts by volume of water and 24 parts by volume of 30% hydrochloric acid. 160 parts of ice and 27 parts by volume of a 23% solution of sodium nitrite are then added, the mixture is stirred for two hours at 0° to 5° C. and then excess nitrous acid is destroyed in the usual way. 18.8 parts of the coupling component of the formula: ##STR11## which has been dissolved in 500 parts by volume of water and 8 parts by volume of 30% hydrochloric acid is then allowed to flow in and the whole is cooled to 0° to 8° C. by adding 250 parts of ice. Coupling is rapidly completed after the pH has been raised to 2.5 with caustic soda solution or sodium acetate. The precipitate deposited is filtered off, washed with water and dried. 28 parts of a reddish brown powder is obtained. In solution the color is orange. The formula of the compound is: ##STR12##

A colored ink consisting of 100 parts of this dye, 400 parts of locust bean ether gum, 200 parts of starch ether and 300 parts of water is applied to transfer paper and dried. Cloth of polyethylene terephthalate or polyamide or a mixture of the two synthetic fibers is pressed onto the printed side of the paper and the paper is heated for thirty seconds at from 190° to 200° C. A full orange dyeing of the synthetic fibers is obtained in this way. The dyeing has good wet and light fastness properties.

Dyes characterized in the following Tables by specifying the substituents and the hue of the dyeing may be prepared and applied to the material to be dyed by analogous methods.

                                      TABLE 1                                      __________________________________________________________________________      ##STR13##                                                                     No.                                                                               R.sup.1                                                                            R.sup.2                                                                            R.sup.3         R.sup.4     Hue                                     __________________________________________________________________________     3  H   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 OCH.sub.3                                                                  yellowish red                           4  "   "   "             CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                         red                                     5  "   "   "                                                                                             ##STR14##    "                                       6  "   "   "                                                                                             ##STR15##    "                                       7  "   "   "             CH.sub.2 CH.sub.2 OCH(CH.sub.3).sub.2                                                        yellowish red                           8  "   "   "             CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           "                                       9  "   "   "             CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7(n)                                                        "                                       10 "   "   "             CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9(n)                                                        "                                       11 "   "   CH.sub.2 CH.sub.2 OCH.sub.3                                                                  CH.sub.2 CH.sub.2 OCH.sub.3                                                                  reddish orange                          12 "   "   C.sub.3 H.sub.7(n)                                                                           CH.sub.2 CH.sub.2 OCH.sub.3                                                                  yellowish red                           13 "   C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 OCH.sub.3                                                                  "                                       14 "   CH.sub.3                                                                           "             CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                "                                       15 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7(n)                                                      "                                       16 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7(i)                                                      "                                       17 "   "   C.sub.3 H.sub.7(n)                                                                           CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                "                                       18 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                         "                                       19 "   H   C.sub.4 H.sub.9(n)                                                                           CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                orange                                  20 "   "   C.sub.2 H.sub.5                                                                              C.sub.2 H.sub.5                                                                              "                                       21 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                         "                                       22 "   CH.sub.3                                                                           "             CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           red                                     23 "   H   "                                                                                             ##STR16##    orange                                  24 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                         "                                       25 "   "   "             CH.sub.2 CH.sub.2 COOCH.sub.3                                                                "                                       26 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.3 H.sub.7(i)                                                      "                                       27 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.6 H.sub.13(n)                                                     "                                       28 "   CH.sub.3                                                                           "             CH.sub.2 CH.sub.2 COOC.sub.6 H.sub.13(n)                                                     yellowish red                           29 "   "   "             CH.sub.2 CH.sub.2 COOCH.sub.3                                                                "                                       30 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                         "                                       31 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.3 H.sub.7(n)                                                      "                                       32 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.3 H.sub.7(i)                                                      "                                       33 "   "   "             CH.sub.2 CH.sub.2 COOC.sub. 4 H.sub.9(n)                                                     "                                       34 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.4 H.sub.9(i)                                                      "                                       35 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.4 H.sub.9(t)                                                      "                                       36 CH.sub.3                                                                           "   "             CH.sub.2 CH.sub.2 COOCH.sub.3                                                                brownish red                            37 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                         "                                       38 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.3 H.sub.7(i)                                                      "                                       39 "   "   CH.sub.2 CH.sub.2 OCH.sub.3                                                                  CH.sub.2 CH.sub.2 COOC.sub.3 H.sub.7(i)                                                      "-40 " " CH.sub.2 CH.sub.2                                                     OCH(CH.sub.3).sub.2 CH.sub.2                                                   CH.sub.2 COOCH.sub.3 "                  41 "   "   C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 OCH(CH.sub.3).sub.2                                                        "                                       42 "   "   "             CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                "                                       43 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                         "                                       44 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7(i)                                                      "                                       45 "   "   "                                                                                             ##STR17##    "                                       46 "   "   "             CH.sub.2 CH.sub.2 OCH.sub.3                                                                  "                                       47 "   "   C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           "                                       48 "   H   "             CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           orange red                              49 "   "   "             CH.sub.2 CH.sub.2 OCH.sub.3                                                                  "                                       50 "   "   "             CH.sub.2 CH.sub.2 OCH(CH.sub.3).sub.2                                                        "                                       51 "   "   "             CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                "                                       52 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                         "                                       53 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7(n)                                                      "                                       54 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7(i)                                                      "                                       55 "   "   "             CH.sub.2 CH.sub.2 COOCH.sub.3                                                                "                                       56 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                         "                                       57 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.3 H.sub.7(n)                                                      "                                       58 "   "   "             CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           "                                       59 H   "   "             CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           orange                                  60 "   "   "             CH.sub.2 CH.sub.2 OCH.sub.3                                                                  "                                       61 "   "   C.sub.4 H.sub.9(n)                                                                           CH.sub.2 CH.sub.2 OCH.sub.3                                                                  "                                       62 C.sub.2 H.sub.5                                                                    "   C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                brownish red                            63 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                         "                                       64 H   C.sub.2 H.sub.5                                                                    "             CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                         reddish orange                          65 "   "   "             CH.sub.2 CH.sub.2 COOCH.sub.3                                                                "                                       66 "   Cl  "             C.sub.2 H.sub.5                                                                              orange                                  67 CH.sub.3                                                                           "   "             C.sub.2 H.sub.5                                                                              "                                       68 H   CH.sub.3                                                                           "                                                                                             ##STR18##    red                                     69 OCH.sub.3                                                                          H   "             C.sub.2 H.sub.5                                                                              "                                       70 "   "   C.sub.3 H.sub.7(n)                                                                           C.sub.3 H.sub.7(n)                                                                           "                                       71 H   OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                              C.sub.2 H.sub.5                                                                              "                                       72 "   "   C.sub.3 H.sub.7(n)                                                                           C.sub.3 H.sub.7(n)                                                                           "                                       73 "   "   CH.sub.2 CH.sub.2 OCH.sub.3                                                                  C.sub.2 H.sub.5                                                                              "                                       74 "   "   C.sub.2 H.sub.5                                                                              CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                         "                                       75 "   "   "             CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                         "                                       76 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CH.sub.2 OCH.sub.3                                                                  CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                         "                                       77 "   "   "             CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7(i)                                                      "                                       78 H   "   "             CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7(i)                                                      yellowish red                           79 "   "   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3                                              CH.sub.2 CH.sub.2 CH.sub.2 COOCH.sub.3                                                       red                                     __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________      ##STR19##                                                                     No. X Y Z  R.sup.2   R.sup.3    R.sup.4    Hue                                 __________________________________________________________________________     80  H H H  H         C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                               orange                              81  " " "  "         "          CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                      "                                   82  " Cl                                                                               "  "         "          CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                      "                                   83  Cl                                                                               " "  "         "          C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                        red                                 84  " Cl                                                                               "  CH.sub.3  "          C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                        "                                   85  H H "  NHCOCH.sub.3                                                                             "          C.sub.2 H.sub.5                                                                           orange                              86  " " "  "         C.sub.3 H.sub.7(n)                                                                        C.sub.3 H.sub.7(n)                                                                        "                                   87  Cl                                                                               " "  "         "          "          red                                 88  " " "  "         C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           "                                   89  Br                                                                               " "  CH.sub.3  C.sub.2 H.sub.5                                                                           CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7(i)                                                   "                                   90  Cl                                                                               " CH.sub.3                                                                          "         "          CH.sub.2 CH.sub.2 OCH.sub.3                                                               "                                   91  " " "  "         "          CH.sub.2 CH.sub.2 OCOCH.sub.3                                                             "                                   92  " " "  "         "          CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                      "                                   93  " " "  "         "          CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                      "                                   94  " " H  NHCOC.sub.2 H.sub.5                                                                      "          C.sub.2 H.sub.5                                                                           "                                   95  " " "  NHCOC.sub.3 H.sub.7(n)                                                                   "          "          "                                   96  " " "                                                                                  ##STR20##                                                                               "          "          "                                   97  H " "  CH.sub.3  "          "          orange                              98  " " "  C.sub.2 H.sub.5                                                                          "          "          "                                   99  " " "  OCH.sub.3 "          "          yellowish                                                                      red                                 100 " " "  CH.sub.3  "          CH.sub.2 CH.sub.2 OCOCH.sub.3                                                             orange                              101 " " "  "         "          CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                      "                                   102 " " "  "         "          CH.sub.2 CH.sub.2 OCOC.sub.3 H.sub.7(n)                                                   "                                   103 " " CH.sub.3                                                                          "         CH.sub.2 CH.sub.2 OCH.sub.3                                                               "          "                                   104 " " "  "         "          CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                      "                                   105 " " "  "         "          CH.sub.2 CH.sub.2 COOCH.sub.3                                                             "                                   106 " " "  "         "          CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                      "                                   107 " " "  "         CH.sub.2 CH.sub.2 OCH(CH.sub. 3).sub.2                                                    CH.sub.2 CH.sub.2 COOCH.sub.3                                                             "                                   108 Cl                                                                               " "  "         CH.sub.2 CH.sub.2 OCH.sub.3                                                               "          red                                 109 " " "  "         "          CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                      "                                   110 " " H  NHCOCH.sub.2 OCH.sub.3                                                                   C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           "                                   111 " " "  NHCOCH.sub.2 OC.sub.2 H.sub.5                                                            "          "          "                                   112 " " "  CH.sub.3  CH.sub.2 CHCH.sub.2                                                                       "          "                                   113 " " "  "         "          CH.sub.2 CH.sub.2 COOC.sub.2 H.sub.5                                                      "                                   114 " " "  NHCOC.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           "                                   115 " " "  NHCOCH(CH.sub.3).sub.2                                                                   "          "          "                                   116 " " "  NHCOC.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 Cl                                                                        C.sub.2 H.sub.4 Cl                                                                        "                                   __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________      ##STR21##                                                                     No.                                                                               R.sup.1                                                                            R.sup.2                                                                            R.sup.3 R.sup.4   Hue                                               __________________________________________________________________________     117                                                                               OCH.sub.3                                                                          CH.sub.3                                                                           C.sub.2 H.sub.5                                                                        CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                     bluish red                                        118                                                                               "   "   "       CH.sub.2 CH.sub.2 OCOCH.sub.3                                                            "                                                 119                                                                               "   "   C.sub.3 H.sub.7(n)                                                                     "         "                                                 120                                                                               "   "   C.sub.4 H.sub.9(n)                                                                     "         "                                                 121                                                                               OC.sub.2 H.sub.5                                                                   H   C.sub.2 H.sub.5                                                                        CH.sub.2 CH.sub.2 OCH.sub.3                                                              red                                               122                                                                               H   OC.sub.2 H.sub.5                                                                   "       "         "                                                 123                                                                               "   "   "       C.sub.2 H.sub.5                                                                          "                                                 124                                                                               "   H   "       C.sub.2 H.sub.4 Cl                                                                       orange                                            125                                                                               "   CH.sub.3                                                                           "       "         reddish orange                                    126                                                                               "   "   CH.sub.2 CH.sub.2 OCH.sub.3                                                            "         "                                                 127                                                                               CH.sub.3                                                                           "   "       "         brownish red                                      128                                                                               H   "   C.sub.2 H.sub.5                                                                        CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7(n)                                                    red                                               129                                                                               "   "   "       CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7(i)                                                    "                                                 130                                                                               "   "   "       CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9(n)                                                    "                                                 131                                                                               "   "   C.sub.3 H.sub.7(n)                                                                     "         "                                                 132                                                                               "   "   "       CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7(i)                                                    "                                                 133                                                                               "   "   "       CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7(n)                                                    "                                                 134                                                                               "   "   "       CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                       "                                                 135                                                                               "   "   "       C.sub.3 H.sub.7(n)                                                                       "                                                 136                                                                               "   "   C.sub.4 H.sub.9(n)                                                                     C.sub.4 H.sub.9(n)                                                                       "                                                 137                                                                               "   "   "       C.sub.4 H.sub.9(i)                                                                       "                                                 138                                                                               "   C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                          "                                                 139                                                                               "   "   C.sub. 3 H.sub.7(n)                                                                    C.sub.3 H.sub.7(n)                                                                       "                                                 140                                                                               "   C.sub.3 H.sub.7(n)                                                                 C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                          "                                                 __________________________________________________________________________ 

I claim:
 1. A dye of the formula ##STR22## in which R¹ is hydrogen,R² is C₁ - to C₄ -alkyl, R³ is C₁ - to C₄ -alkyl or C₂ - to C₄ -alkyl substituted by C₁ - to C₆ -alkoxy, C₁ - to C₄ -alkanoyl, chloroacetyl, chloropropionyl, methoxyacetyl, ethoxyacetyl or C₁ - to C₄ -alkoxycarbonyl, R⁴ is C₁ - to C₆ -alkyl or C₂ - to C₄ -alkyl substituted by C₁ - to C₄ -alkoxy and Z is hydrogen or methyl.
 2. A dye according to claim 1 of the formula ##STR23## in which R⁹ is C₁ - to C₄ -alkyl,R⁷ is C₂ - to C₄ -alkyl or C₁ - to C₄ -alkoxy-C₂ - or C₃ -alkyl and R⁸ is C₂ - to C₄ -alkyl or C₁ - to C₄ -alkoxy-C₂ - to C₄ -alkyl.
 3. A dye according to claim 2 of the formula ##STR24## in which R⁷ and R⁸ have the meanings given for claim
 2. 4. The dye according to claim 1 of the formula ##STR25##
 5. The dye according to claim 1 of the formula ##STR26##
 6. The dye according to claim 1 of the formula ##STR27##
 7. The dye according to claim 1 of the formula ##STR28## 